2026-04-13T02:57:59Zhttps://recercat.cat/oai/request
oai:recercat.cat:20.500.14342/46462025-05-28T23:43:19Zcom_2072_482405com_2072_183628col_2072_482414
RECERCAT author Chen, Wei W. author Artigues Cladera, Margalida author Font-Bardia, Mercè author Cuenca, Ana Belen author Shafir, Alexandr 2023-06-28 1520-5126 http://hdl.handle.net/20.500.14342/4646 https://doi.org/10.1021/jacs.3c02406 In the context of the ever-growing interest in the cyclic diaryliodonium salts, this work presents synthetic design principles for a new family of structures with two hypervalent halogens in the ring. The smallest bis-phenylene derivative, [(C6H4)2I2]2+, was prepared through oxidative dimerization of a precursor bearing the ortho-disposed iodine and trifluoroborate groups. We also report, for the first time, the formation of cycles containing two different halogen atoms. These present two phenylenes linked by hetero-(I/Br) or -(I/Cl) halogen pairs. This approach was also extended to the cyclic bis-naphthylene derivative [(C10H6)2I2]2+. The structures of these bis-halogen(III) rings were further assessed through X-ray analysis. The simplest cyclic phenylene bis-iodine(III) derivative features the interplanar angle of ∼120°, while a smaller angle of ∼103° was found for the analogous naphthylene-based salt. All dications form dimeric pairs through a combination of π–π and C–H/π interactions. As the largest member of the family, a bis-I(III)-macrocycle was also assembled using the quasi-planar xanthene backbone. Its geometry enables the two iodine(III) centers to be bridged intramolecularly by two bidentate triflate anions. In a preliminary manner, the interaction of the phenylene- and naphthalene-based bis-iodine(III) dications with a new family of rigid bidentate bis-pyridine ligands was studied in solution and the solid state, with an X-ray structure showing the chelating donor bonding to just one of the two iodine centers. eng © L'autor/a Attribution 4.0 International Aromatic compounds Chemical structure Group 17 compounds Reaction products Salts Compostos aromàtics Estructura química Elements químics Reactivitat (Química) Sals Cyclic Homo- and Heterohalogen Di-λ3-diarylhalonium Structures info:eu-repo/semantics/article